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Title: Model-Based Analysis of the Limiting Mechanisms in the Gas-Phase Oxidation of HCl Employing an Oxygen Depolarized Cathode

Abstract

The electrochemical oxidation of HCl to Cl2 plays an important role in the production of polycarbonates and polyurethanes. Recently, the gas-phase oxidation of HCl proved to be significantly more efficient than the current state-of-the-art process based on the oxidation of hydrochloric acid. In experimental investigations of this gas-phase reactor, a limiting current can be observed that is so far not understood but impedes the overall reactor performance. In the present work, a nonisothermal multiphase agglomerate model is developed to investigate the underlying reasons for this limiting behavior in more detail. It is shown that the thermal management of the cell plays a significant role and that minor changes to its thermal resistance lead to the limiting behavior being caused by either flooding of the cathode or dehydration of the membrane and anode. An optimization of operational and structural parameters of the cell based on these insights leads to an increase in the limiting current by more than 90%. Interestingly, under these conditions a third phenomenon, the rate determining Tafel step in the microkinetic reaction mechanism of the HCl oxidation, limits the overall reactor performance. These insights harbor the potential for enormous energetic savings in this industrially highly relevant process.

Authors:
; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1582502
Alternate Identifier(s):
OSTI ID: 1760201
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online) Journal Volume: 167 Journal Issue: 1; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Bechtel, Simon, Vidaković-Koch, Tanja, Weber, Adam Z., and Sundmacher, Kai. Model-Based Analysis of the Limiting Mechanisms in the Gas-Phase Oxidation of HCl Employing an Oxygen Depolarized Cathode. United States: N. p., 2020. Web. doi:10.1149/1945-7111/ab6449.
Bechtel, Simon, Vidaković-Koch, Tanja, Weber, Adam Z., & Sundmacher, Kai. Model-Based Analysis of the Limiting Mechanisms in the Gas-Phase Oxidation of HCl Employing an Oxygen Depolarized Cathode. United States. doi:10.1149/1945-7111/ab6449.
Bechtel, Simon, Vidaković-Koch, Tanja, Weber, Adam Z., and Sundmacher, Kai. Wed . "Model-Based Analysis of the Limiting Mechanisms in the Gas-Phase Oxidation of HCl Employing an Oxygen Depolarized Cathode". United States. doi:10.1149/1945-7111/ab6449.
@article{osti_1582502,
title = {Model-Based Analysis of the Limiting Mechanisms in the Gas-Phase Oxidation of HCl Employing an Oxygen Depolarized Cathode},
author = {Bechtel, Simon and Vidaković-Koch, Tanja and Weber, Adam Z. and Sundmacher, Kai},
abstractNote = {The electrochemical oxidation of HCl to Cl2 plays an important role in the production of polycarbonates and polyurethanes. Recently, the gas-phase oxidation of HCl proved to be significantly more efficient than the current state-of-the-art process based on the oxidation of hydrochloric acid. In experimental investigations of this gas-phase reactor, a limiting current can be observed that is so far not understood but impedes the overall reactor performance. In the present work, a nonisothermal multiphase agglomerate model is developed to investigate the underlying reasons for this limiting behavior in more detail. It is shown that the thermal management of the cell plays a significant role and that minor changes to its thermal resistance lead to the limiting behavior being caused by either flooding of the cathode or dehydration of the membrane and anode. An optimization of operational and structural parameters of the cell based on these insights leads to an increase in the limiting current by more than 90%. Interestingly, under these conditions a third phenomenon, the rate determining Tafel step in the microkinetic reaction mechanism of the HCl oxidation, limits the overall reactor performance. These insights harbor the potential for enormous energetic savings in this industrially highly relevant process.},
doi = {10.1149/1945-7111/ab6449},
journal = {Journal of the Electrochemical Society (Online)},
number = 1,
volume = 167,
place = {United States},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/1945-7111/ab6449

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